JP2002167526A - Putty or primer surfacer composition and its curing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photo-setting putty or primer surfacer composition which realizes the shortening of the time of working steps and is improved in the tight adhesion to the surface of a base material, and to provide its curing method. SOLUTION: The putty or primer surfacer composition contains (A) a radical- polymerizable resin, (B) a radical-polymerizable unsaturated compound, (C) a photopolymerization initiator having photosensitivity in a visible light region and/or a polymerization initiator comprising a combination of an organoboron compound of formula (1) (wherein R1 to R4 are each independently an alkyl, an aryl, an aralkyl, an alkenyl, an alkynyl, a silyl, a heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group; and Z+ is a cation with an acidic compound, and (D) a filler. The curing method comprises irradiating the composition with a visible light in a specified wavelength region.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a putty or primer surfacer composition which is rapidly cured by light irradiation and has excellent adhesion to a substrate, and a curing method.

[0002]

2. Description of the Related Art Putties, primers and primer surfacers are used for various repairs in the industrial field. For example, vehicles such as automobiles and molded articles such as plastics may be damaged by molding failure or external force during molding. In such a case, as one of the repair methods for the damaged part, generally putty is applied to the damaged part and hardened, then the surface is polished smoothly, and if necessary, a primer, a primer surfacer is applied, and then a finish coating etc. It has been repaired.

[0003] In this series of repair work, the putty treatment and the primer surfacer coating process require a long time for curing, and after curing, it is necessary to smoothly polish the coated surface for each coating in order to obtain a good surface condition. These processes require a great deal of time and effort.

As a putty generally used for repair applications, a two-pack room temperature-curing putty or a heat-curing putty mainly made of an organic peroxide using an unsaturated polyester resin or the like is used. Since it is a mold, a mixing operation is required, and it is necessary to adjust the amount of the organic peroxide depending on the environmental temperature, which complicates the operation. In addition, when the curing time is shortened, the work time is also shortened, so that skillful work is required, poor curing of the coating film due to mixing mistakes, the entrainment of air due to the mixing work, the curing after curing, It has many potential problems such as blistering and thinning of the coating. In addition, when improvement in adhesion to a substrate and improvement in surface smoothness are required, a primer or a primer surfacer is used, but a generally used primer or primer surfacer uses a non-reactive diluent. Lacquer system, alkyd system, urethane system, epoxy system.
At present, it takes a long time for coating film drying and curing time, and it is necessary to further perform a heat treatment step and the like in order to shorten the curing time.

On the other hand, as a method for improving the mixing mistake, the mixing operation, and the point that requires a long time for curing, a one-pack type ultraviolet curable type, visible light curable type, and near infrared light curable putty have been proposed. I have. With this putty, there is no mixing work and there is no restriction on the pot life, but there is a problem in adhesion to the base, because the curing difference between the surface and the interior causes a large curing shrinkage and internal stress of the coating film. .

[0006] Japanese Patent Application Laid-Open No.
In JP-A-137089 and JP-A-09-176517, improvements are made by adding a phosphoric acid group-containing compound. However, since these compounds have no reactive group, they remain in the cured product system and have blister resistance. Properties and adhesion to the substrate were insufficient.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention is a light-curing type putty composition having a reduced working time and improved adhesion to a substrate surface, or a surface smoothness having a reduced working time. And a method for curing the same.

[0008]

The present invention provides [1].
(A) unsaturated polyester resin, vinyl ester resin,
Polyester (meth) acrylate, urethane (meth)
One or more radical polymerizable resins selected from acrylate resins: 100 parts by weight, (B) a radical polymerizable unsaturated compound having one or more carboxyl groups in the molecule: 1 to 1
100 parts by weight, (C) a photopolymerization initiator having photosensitivity in the visible light region and / or a polymerization initiator which is a combination of an organic boron compound represented by the general formula (1) and an acidic compound:
0.01 to 10 parts by weight and (D) filler: 0.1 to 30
A putty or primer surfacer composition, characterized by containing 0 parts by weight,

[0009]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, Alkyl group, substituted aryl group,
Substituted allyl group, substituted aralkyl group, substituted alkenyl group,
Represents a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a cation)

[2] A polymerization initiator obtained by combining the polymerization initiator (C) with an organic boron compound and an acidic compound, and further with a hexaarylbiimidazole compound [1].
Putty or primer surfacer composition, [3].
The putty or primer surfacer composition according to any one of [2] and [3], wherein the acidic compound is a latent acid generator that generates an acid by at least one action of light irradiation, heating, moisture and oxygen in the air. [4]. Light irradiation, heating,
The putty or primer surfacer composition of [3], wherein the latent acid generator that generates an acid by at least one action of moisture and oxygen in the air is a sulfonium compound that generates an acid by light irradiation and / or heating, [ 5). The putty or primer surfacer composition according to claim 1, wherein the photopolymerization initiator having photosensitivity in the visible light region is a (bis) acyl phosphine oxide type, and [6]. Any putty or primer surfacer composition of (1) to (5), and (7).
The putty or primer surfacer composition according to any one of [1] to [5], wherein the putty or primer surfacer composition is irradiated with light having a light intensity of 20 mw / cm ² or more in a wavelength region of 380 to 450 nm and cured. This is a method for curing the composition.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As the resins used in the present invention, at least one of unsaturated polyester resin, vinyl ester resin, polyester (meth) acrylate resin and urethane (meth) acrylate resin is used. . The unsaturated polyester resin used in the present invention,
A product obtained by dissolving a condensation product (unsaturated polyester) obtained by an esterification reaction between a polyhydric alcohol and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) in a polymerizable monomer such as styrene, Polyester Resin Handbook "(published by Nikkan Kogyo Shimbun, 1988) or" Paint Glossary "(edited by The Coloring Materials Association, published in 1993).

The unsaturated polyester used as the raw material for the unsaturated polyester resin may be one produced by a known method. Specifically, a polybasic acid having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid or an anhydride thereof and fumaric acid, maleic acid, itaconic acid And the like, and a polymerizable unsaturated polybasic acid or an anhydride thereof as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2
Manufactured by reacting a polyhydric alcohol such as -dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A, or a propylene oxide adduct of bisphenol A as an alcohol component. It is.

The vinyl ester resin used in the present invention is also called an epoxy acrylate resin, and generally has a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. A compound having a polymerizable unsaturated bond (vinyl ester) formed by a ring-opening reaction of is dissolved in a polymerizable monomer such as styrene, and is referred to as "Polyester Resin Handbook" (published by Nikkan Kogyo Shimbun, 1988). Or “Paint Glossary” (edited by the Coloring Materials Association, 1993)
This is a resin described in the following publication. The vinyl ester used as a raw material of the vinyl ester resin (epoxy acrylate resin) is produced by a known method, and is obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid. Α, β-unsaturated carboxylic acid ester group having an epoxy group on a saturated polyester or unsaturated polyester having a terminal carboxyl group obtained from an epoxy (meth) acrylate or a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyhydric alcohol Is a polyester (meth) acrylate of a saturated polyester or an unsaturated polyester obtained by reacting Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether, its high molecular weight homologues, and novolak-type polyglycidyl ethers.

Examples of the saturated dicarboxylic acid used for the terminal carboxyl polyester include dicarboxylic acids having no active unsaturated group, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid and sebacic acid. As the unsaturated dicarboxylic acid, a dicarboxylic acid having an active unsaturated group, for example, fumaric acid,
Maleic acid, maleic anhydride, itaconic acid and the like can be mentioned. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-
Propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol,
Polyhydric alcohols such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A are exemplified.

Polyester (meth) acrylate resins include (1) polyesters having terminal carboxyl groups obtained from saturated polybasic acids and / or unsaturated polybasic acids and polyhydric alcohols, and α, β-unsaturated carboxylic acid ester groups. (2) reacting a hydroxyl group-containing acrylate with (2) a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol; (Meth) acrylate resin obtained by reacting (meth) acrylic acid with a (meth) acrylate resin obtained by reacting (3) a polyester having a terminal hydroxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol ( (Meth) acrylate resin.

The saturated polybasic acid used as a raw material of the polyester (meth) acrylate has a polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid and sebacic acid. No polybasic acid or its anhydride and fumaric acid,
Examples thereof include polymerizable unsaturated polybasic acids such as maleic acid and itaconic acid and anhydrides thereof. Further, as the polyhydric alcohol component, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
1,2-butanediol, 1,3-butanediol,
1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-
Examples thereof include dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A. Glycidyl methacrylate is a representative example of the α, β-unsaturated carboxylic acid ester having an epoxy group used in the production of polyester (meth) acrylate.

The urethane (meth) acrylate resin is
It is a known oligomer resin obtained by reacting a polyisocyanate with a polyol such as a polyether polyol, a polyester polyol, a polyacryl polyol and a hydroxyalkyl acrylate.

Unsaturated polyesters used for resins, etc.
As the vinyl ester, polyester (meth) acrylate and urethane (meth) acrylate, those having an unsaturated group equivalent (molecular weight per unsaturated group) of about 50 to 5000 are used.

The unsaturated polyester resin, vinyl ester resin, polyester (meth) used in the present invention
The acrylate resin and the urethane (meth) acrylate resin generally have an unsaturated group such as styrene monomer or methyl (meth) acrylate in the unsaturated polyester, vinyl ester, polyester (meth) acrylate, or urethane (meth) acrylate. The compound which has the compound which has. Specific examples of the styrene monomer and the compound having an unsaturated group other than methyl (meth) acrylate include α-, o-, mp-alkyl, nitro, cyano, amide, ester derivatives of styrene, chlorostyrene, vinyl Styrene monomers such as toluene and divinylbenzene, butenes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid i-propyl, (meth) acrylic acid-
n-butyl, -sec-butyl (meth) acrylate,
Tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Lauryl acrylate, dodecyl (meth) acrylate,
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate,
Isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate,
Naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate,
Piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, Phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1- (meth) acrylic acid
Trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-i-propyl (meth) acrylate,
Triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid- (Meth) acrylates such as 2-hydroxypropyl diethyl citraconic acid, diethyl maleate, diethyl fumarate,
And unsaturated dicarboxylic acid diesters such as diethyl itaconate.

In the present invention, as the compound having an unsaturated group, a (meth) acrylate compound having two or more (meth) acryloyl groups in the molecule may be used, and known compounds can be used. Specific examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, glycerin di (meth) acrylate, 2
-Hydroxy-3-acryloyloxypropyl (meth)
Examples include (meth) acrylic acid esters of various glycols such as acrylate and trimethylolpropane tri (meth) acrylate, and are not limited thereto. In addition, monomers and oligomers having radically polymerizable unsaturated groups may also be used. Can be used. These may be used alone or in combination of two or more, and a non-reactive diluent may be used in combination as long as the properties are not impaired.
Examples of the non-reactive diluent include organic solvents.

The compound having an unsaturated group blended in the resin or the like of the present invention is important for lowering the viscosity of the resin and improving the hardness, strength, weather resistance, water resistance and the like. Is determined according to the type and the amount of addition, but is preferably 10 to 250 parts by weight, preferably 20 to 1 part by weight based on 100 parts by weight of the unsaturated polyester, vinyl ester, polyester (meth) acrylate and urethane (meth) acrylate.
00 parts by weight are used. If the amount used is less than 10 parts by weight,
Due to the high viscosity, workability and filler filling property deteriorate, and 250
If the amount exceeds the weight part, sufficient coating film hardness cannot be obtained, and various physical properties are insufficient, which is not preferable as a composition.

The radically polymerizable unsaturated compound having at least one carboxyl group in the molecule used in the present invention includes (meth) acrylic acid, crotonic acid, cinnamic acid,
Reaction products of sorbic acid, maleic acid, fumaric acid, itaconic acid, dicyclopentadiene and polycarboxylic acid compounds (for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) And the like half ester. Further, a part of the radically polymerizable compound having one or more carboxyl groups used in the present invention is replaced with a saturated monobasic acid such as acetic acid, propionic acid or other acidic compounds as long as the gist of the present invention is not impaired. Is also good. In the present invention, oligomers having a carboxyl group at the terminal may be used. In this case, those having a small molecular weight are desirable, and those having a number average molecular weight of 500 or less are desirable.

The amount of the radically polymerizable unsaturated compound having at least one carboxyl group in the molecule used in the present invention is generally 1 to 100 parts by weight per 100 parts by weight of the resin or the like.
Parts by weight, preferably 3 to 50 parts by weight. If the amount of the radically polymerizable unsaturated compound is less than 1 part by weight, the adhesion to the substrate tends to be insufficient. If the amount exceeds 100 parts by weight, the storage stability is adversely affected. When an oligomer having a terminal carboxyl group is used, the acid value is 5 KOHmg / g.
Above, preferably 10 KOHmg / g or more.

As the photopolymerization initiator having photosensitivity in the visible light region used in the present invention, a known visible light polymerization initiator can be used. In the present invention, visible light is 380 to 380.
Refers to a light beam of 780 nm. As a visible light polymerization initiator having photosensitivity in the visible light region, for example, Yamaoka et al., “Surface”,
27 (7), p. 548 (1989); Sato et al., "3rd Polymer Material Forum Abstracts", 1B, p. 18 (1
994), a visible light polymerization initiator alone such as camphorquinone, benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, bispentadienyltitanium-di (pentafluorophenyl), and an organic peroxide catalyst / Dye system, diphenyliodonium salt / dye, biimidazole / keto compound, hexaarylbimidazole compound / hydrogen donating compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye, and JP-B-45-37377 Known complex initiator systems such as the described hexaarylbiimidazole / radical generators can be mentioned.

In the present invention, a (bis) acyl phosphine oxide-based photopolymerization initiator having photosensitivity in the visible light region is preferably used. The acylphosphine oxide used as a photopolymerization initiator in the present invention is represented by the general formula (2) or (3).

[0027] (Wherein, R ^{1 to} R ³ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or an alkynyl group)

[0028] (Wherein, R ^{4 to} R ⁶ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, or a heterocyclic group)

Specific examples of the bisacylphosphine oxide compound of the general formula (2) used in the present invention include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide and bis (2,6-dichlorobenzoyl) −
2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylphosphine oxide, bis (2,6- Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2 6-dichlorobenzoyl)
-4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,2-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -dodecylphosphine oxide, bis (2,6-di Chlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,
4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-phenylphosphine oxide,
Bis (2-methyl-1-naphthoyl) -4-biphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine Oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-methoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)
And -2,4,4-trimethylpentylphosphine oxide.

Specific examples of the acylphosphine oxide compound of the general formula (3) used in the present invention include 2,2.
4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-diphenylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,3,5,6
-Tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6
-Methylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,8-dimethylnaphthalene-1-carbonyl-diphenylphosphine oxide, 1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl-phenylphosphinic acid methyl ester, and the like.

Specifically, for example, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one (trade name: D
arocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl)
75% of 2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.)
Trade name Irgacure-1 mixed at a ratio of% / 25%
700 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (Ciba Special) Tea Chemicals Co., Ltd.
(Trade name) Irgacure 1800 (Ciba Specialty Chemicals Co., Ltd.) mixed at a ratio of 75% / 25%, and Irgacure 1850 (Ciba Specialty) mixed at a ratio of 50% / 50% Chemicals Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, Ciba Specialty Chemicals Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenyl Phosphine oxide (trade name Lucirin)
TPO, manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Da)
rocur1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name Lucirin)
Darocur 4265 (trade name) obtained by mixing TPO and BASF (trade name) at a ratio of 50% / 50%.

The photopolymerization initiator used in the present invention is 380
Any photosensitizer may be used as long as it has photosensitivity in the wavelength range of ７780 nm, and the above photopolymerization initiators may be used in combination.
These initiators have photosensitivity even in the visible light region, are excellent in light transmittance, and are cleaved by light irradiation to generate acyl radicals and phosphinoyl radicals. It is said that the polymerization initiation efficiency is higher than that.

The amount of the photopolymerization initiator sensitive to visible light is 0.05 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resin.
More than one species can be used in combination. If the amount of the photopolymerization initiator is too small, the surface cannot be dried sufficiently.If the amount of the photopolymerization initiator is too large, the cured product is economically disadvantageous. The physical properties of the material decrease.

In the present invention, a known organic peroxide may be used together with these photopolymerization initiators. For example, ketone peroxide, peroxyketal, hydroperoxide, diallyl peroxide and azo compound can also be used. . Particularly, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide and the like are effective.

In the present invention, a known radical polymerization inhibitor such as a quinone, an active hydrogen donor chain transfer agent or a known oxygen is used to adjust the curing time of the resin to which the photopolymerization initiator is added and to ensure surface drying properties. Tertiary amines, stannous salts, and other compounds that are easily oxidized by oxygen may be added as a removing agent.

As the organic boron compound used in combination with the acidic compound as the photopolymerization initiator of the present invention, the following general formula (1)

[0037]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, Alkyl group, substituted aryl group,
Substituted allyl group, substituted aralkyl group, substituted alkenyl group,
Represents a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a cation).

Examples of the cation “Z ⁺ ” include quaternary ammonium cations, quaternary pyridinium cations, quinolinium cations, diazonium cations, and tetrazonium cations which are insensitive to visible light and near-infrared light. Ions, kissonium cations, (oxo) sulfonium cations, metal cations such as sodium, potassium, lithium, magnesium and calcium, and cations on oxygen atoms such as flavylium and pyranium salts (organic)
Examples include compounds, carbon cations such as tropinium and cyclopropylium, halogen cations such as iodonium, and cations of metal compounds such as arsenic, cobalt, palladium, chromium, titanium, tin and antimony.

Examples of the acidic compound used in combination with the above-mentioned organic boron compound include, for example, inorganic acids generally known as Bronsted acids, for example, hydrochloric acid, sulfuric acid, and the like.
Such as nitric acid, or organic acids such as acetic acid and propionic acid,
Examples include carboxylic acids such as maleic acid, adipic acid, (meth) acrylic acid, benzoic acid, and phthalic acids, and sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Compounds having a hydroxyl group such as phenols and alcohols, compounds having a mercapto group such as various thiols, and substances capable of forming a covalent bond by receiving an electron pair known as a Lewis acid, such as aluminum chloride, stannic chloride, Boron chloride, boron tribromide, or the like can be used. These acids are described in detail, for example, in "Organic Chemistry", 3rd edition, by Morrison Boyd. In addition, a substance having an acidic active site on a solid surface such as an acidic ion exchange resin, carbon black, and alumina, or an acidic gas compound such as hydrogen chloride and sulfurous acid gas can also be used. Among these acidic compounds, acidic compounds having a polymerizable unsaturated group such as (anhydride) maleic acid, fumaric acid, or their half esters, (meth) acrylic acid, and itaconic acid, or oligomers having their functional groups Alternatively, polymers and the like are suitably used.

As the acidic compound used in the present invention, a latent acidic compound which itself is not an acidic substance itself but is decomposed or reacted by heating, the action of moisture in the air, oxygen or the like to generate an acidic compound is also used. . Substances that decompose upon irradiation with light to generate an acidic compound are also known. For example, a compound called a photocationic polymerization initiator also corresponds to the photolatent acidic compound used in the present invention. Various compounds such as diazonium compounds, sulfonium compounds, and iodonium compound metal complex compounds are known as photocationic polymerization initiators.
A detailed description can be found on page 5, October 2005, page 5, "Applications and Markets of UV / EB Curing Technology", page 78, published by CMC 1989. Among these compounds to be referred to as latent acidic compounds, compounds that generate an acid by light or heat are desirable in consideration of availability, economy, stability in a composition, operability, and the like. An organic sulfonium compound which generates an acid by heating, and which is decomposed by heating to generate an acid is more preferable. This organic sulfonium compound generally has three substituents (an alkyl group,
It is composed of an ion pair of a sulfonium cation moiety having an aryl group) and a counter anion. From the viewpoint of stability of the compound, ability to generate an acidic compound, acid strength of the generated acidic compound, and the like. It is desirable that at least one of the substituents of the sulfonium salt is an aryl group such as a (substituted) phenyl group and a (substituted) naphthyl group. For example, preferred compounds include sulfonium compounds having a cation moiety such as triphenylsulfonium and diphenylsulfonium. When the pot life of the resin composition containing the initiator is required to be sufficiently long, for example, when the organic boron compound and the acidic compound start to react when the initiator is compounded, Since it is not preferable, it is desirable to use an acidic compound as a latent acidic compound by stimulus such as heat or light.

When light is irradiated by combining a hexaarylbiimidazole compound with an organic boron compound and an acidic compound, curing is further promoted, and a remarkable effect is obtained.
As the hexaarylbiimidazole compound, specifically, bis (2,4,5-triphenyl) imidazole,
Bis (2-o-chlorophenyl-4,5-diphenyl)
Imidazole, bis (2-o, p-dichlorophenyl-
4,5-diphenyl) imidazole, bis (2-o-bromophenyl-4,5-diphenyl) imidazole and the like can be mentioned. The hexaarylbimidazole compound is described in detail in JP-B-41-3545.

The optimal amount of the polymerization initiator in which the organic boron compound is combined with the (latent) acidic compound and / or hexaarylbiimidazole varies depending on the type of the resin and the like, the type, the amount and the thickness of the fiber material. However, it is generally 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, per 100 parts by weight of the resin or the like. If the amount of the polymerization initiator composition is less than 0.01 part by weight, the polymerization tends to be insufficient, and if the amount exceeds 20 parts by weight, it is economically disadvantageous and the physical properties of the cured product are deteriorated. When the resin or the like contains an acidic compound in advance, maleic acid, fumaric acid, or their half esters, (meth) acrylic acid, itaconic acid, An oligomer or a polymer having a carboxyl group of the carboxylic acid may be used, or a resin or the like added with an arbitrary acidic compound may be used. In this case, the acid value of the unsaturated polyester resin or vinyl ester resin is 0.1 to 100 mgKOH / g, preferably 5 to 50 mgKOH / g.

The composition ratio of the organic boron compound and the (latent) acidic compound in the polymerization initiator is 0.1 / 5 to 5/5 by weight.
0.1, preferably 0.5 / 5 to 5 / 0.5. When the ratio of the organic boron compound / (latent) acidic compound is too small, the curing cannot be sufficiently performed, and when the ratio of the organic boron compound / (latent) acidic compound is too large, the economical efficiency becomes low. In addition to this, the physical properties of the cured product are reduced. In addition, when hexaarylbiimidazole is combined with an organic boron compound and an acidic compound in order to achieve faster curing, the ratio of the organic boron compound / hexaarylbiimidazole is 0.1 / 5 to 5/5 by weight.
0.1, preferably 0.5 / 5 to 5 / 0.5. If the ratio of hexaarylbiimidazole is too small, the effect is not exhibited. If the ratio is too large, it is economically disadvantageous and the pot life under visible light is shortened, and the physical properties of the cured product are reduced. A decrease occurs.

The composition of the present invention may be used in combination with a known coupling agent for improving the adhesion to a substrate. Examples of the coupling agent include a silane coupling agent and a silane coupling agent.
Titanate-based coupling agents, zirconate-based coupling agents, organoaluminum-based coupling agents, and the like can also be used in combination.

The amount of the coupling agent used in the present invention is generally from 0.1 to 30 parts by weight, preferably from 0.5 to 30 parts by weight, based on 100 parts by weight of resin and the like. To 10 parts by weight. When the amount is less than 0.1 part by weight, no effect is obtained, and when the amount is more than 30 parts by weight, curing is likely to be insufficient, and there is a possibility that adhesion may be impaired.

The filler in the composition of the present invention includes an inorganic filler and an organic filler. As the inorganic filler used in the present invention, for example, calcium carbonate, magnesium carbonate,
Barium sulfate, aluminum silicate, calcium silicate, titanium oxide, aluminum hydroxide, talc, kaolin, clay, silica, glass beads, glass balloon,
Glass powder, metal powder, metal fiber, diatomaceous earth, etc. can be used, but are not limited thereto, organic fillers such as other resin powders having the same action as these, inorganic and organic short-circuits of several millimeters or less. Fibers can be used to the extent that they do not affect cure. Such fillers are disclosed in
No. 271373, JP-A-57-10656 and the like.

The amount of the filler used in the present invention is generally 0.1 to 300 parts by weight, preferably 0.5 to 200 parts by weight, and more preferably 0.1 to 300 parts by weight, per 100 parts by weight of the resin and the like. 5 to 150 parts by weight. The amount of filler used is 0.1
If the amount is less than 300 parts by weight, the abrasiveness tends to decrease.If the amount is 300 parts by weight or more, the fluidity of the resin or the like decreases, the ironing property, the spraying property, the curing of the coating film tend to be insufficient, and the adhesion, Durability may be reduced.

The filler used in the present invention can also be used as a thixotropic agent. As the thixotropic agent, for example, inorganic powders such as silica powder, mica powder, calcium carbonate powder,
There are short fiber asbestos and the like, and in the organic system, there is hydrogenated castor oil and the like. The thixotropic agent is used for the fluidity, adhesion, troweling property of the putty and the primer surfacer, and for preventing the sedimentation of the filler. In particular, fine silica powder which is a silica powder type thixotropic agent is preferably used. Further, a thixotropic aid or the like may be used in combination.

When the filler is used as a thixotropic agent, the amount used is generally 0.1 to 2 parts by weight per 100 parts by weight of resin or the like.
0 parts by weight, preferably 0.5 to 15 parts by weight. If the amount of the thixotropic agent is less than 0.1 part by weight, sufficient thixotropic properties cannot be obtained, and sedimentation of the filler cannot be prevented. There is a possibility that the properties may be lowered and the curing may be insufficient, and the adhesion may be impaired.

In the present invention, a coloring pigment can be used as required. For example, titanium-based, carbon black, iron oxide-based, phthalocyanine-based, and azo-based can be used. In the present invention, an additive such as paraffin wax may be added for the purpose of further improving the drying property. Specific examples include paraffin wax having a melting point of about 40 to 80 ° C. and BYK.
-S-750, BYK-S-740, BYK-LP-S
6665 (manufactured by BYK-Chemie KK) and the like, and those having different melting points may be used in combination. The amount of addition is usually 0.1 to 3.0 parts by weight based on 100 parts by weight of the resin. The putty composition and the primer surfacer composition of the present invention include, as a substrate surface, zinc, iron, a metal surface such as aluminum, a thermosetting plastic surface, a thermoplastic plastic surface, a concrete surface, wood, various kinds of vehicles such as ceramics, It can be used for repairing molded products and structures, jointing, etc.

The putty composition of the present invention can be applied by a conventionally known method, can be applied several millimeters or more without sagging by a single application with a spatula, and can be irradiated with visible light. After hardening and smooth polishing of the surface, a top coat can be applied. Further, after the putty composition of the present invention is cured, the photocurable primer surfacer composition of the present invention is applied before topcoating, and cured by irradiating visible light, and a topcoat can be applied. . As the primer surfacer, generally used primer surfacers such as lacquer type, urethane type, alkyd type and epoxy type can also be used. For the top coat after curing the putty or primer surfacer composition of the present invention, commonly used urethane-based, fluorine-based, organic solvent-based such as acrylic lacquer-based, water-based top-coat paints are particularly limited. Can be used without.

The light source for light irradiation used in the present invention may be any light source that emits light in the wavelength region of the visible light range, such as a mercury lamp, a metal halide lamp, a xenon lamp, a halogen lamp, and near infrared light. Lamps, sodium lamps, incandescent lamps, sunlight lamps, sunlight, and the like can be used. Further, various lamps can be used in combination. For outdoor work, sunlight is particularly effective. Furthermore, when the thickness of the putty or primer surfacer composition is large, it is difficult to completely cure the composition, and when an organic peroxide or the like is used in combination, a light source that emits a large amount of heat in a long wavelength region at a wavelength of 380 nm or more in a long wavelength region. Light is effective, and metal halide lamps, halogen lamps, near-infrared lamps, infrared lamps and the like are effective.

The irradiation time of the lamp varies depending on the effective wavelength of the light source, the output, the irradiation distance, the thickness of the putty and the primer composition, and the amount of the filler, and therefore cannot be specified unconditionally. May be set to 0.05 hours or more. In the present invention, it is preferable that the above putty or primer surfacer composition is cured by irradiating light having an illuminance of 20 mw / cm ² or more in a wavelength region of 380 to 450 nm.

[0055]

The present invention will be described more specifically with reference to the following examples and comparative examples. Note that “parts” and “%” in each of Examples and Comparative Examples are based on weight.

Examples 1-4 and Comparative Examples 1-2 The following putty compositions were prepared and cured on test plates.
The performance of the putty coating was evaluated. <Preparation of Putty Composition> In Example 1, a vinyl ester resin [trade name: Lipoxy R-802: manufactured by Showa Polymer Co., Ltd.]:
100 parts, acrylic acid [manufactured by Osaka Organic Chemical Industry Co., Ltd.]: 5
100 parts of the mixture consisting of 3 parts by weight of the silica thixotropic agent A
EROSIL200 [manufactured by Nippon Aerosil Co., Ltd.]: 4 parts,
Thixotropic auxiliary BYK R605 [manufactured by BYK Japan KK]: 1.6 parts, acylphosphine oxide-based photopolymerization initiator having photosensitivity up to the visible light region [trade name Irgacure-819: manufactured by Ciba Specialty Chemicals, Hereinafter, it is referred to as I-819. ]: 2.0 parts, trimethylolpropane triacrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., hereinafter referred to as TMP3A]: 5 parts, 2-hydroxyethyl methacrylate [product name Light Ester H]
O, manufactured by Kyoeisha Chemical Co., Ltd., referred to as 2-HEMA]: 10
Parts, talc: 50 parts, and calcium carbonate: 50 parts, and the mixture was stirred and mixed with a high-speed dissolver for 20 minutes to obtain a putty composition.

In Examples 2 to 4 and Comparative Examples 1 and 2, the composition of the resin and the polymerization initiator in Example 1 was changed to the composition shown in Table 1 and the putty composition was obtained by the same operation as in Example 1. I got something. In Table 1, lipoxy FM
-1600 is urethane methacrylate Rigolac FK-
2000 is an unsaturated polyester resin [Showa High Polymer Co., Ltd.
And acrylic ester ML are 2-methacryloyloxyethyl maleate [manufactured by Mitsubishi Rayon Co., Ltd.], DP4
Is dibutyl phosphate (manufactured by Daihachi Chemical Co., Ltd.),
Methacrylic acid used was from Kuraray Co., Ltd. PB3 is tetra-n-butylammonium triphenyl-n-butylborate (manufactured by Showa Denko KK) as an organic boron compound, and CI-2855 is organic sulfonium hexafluoride as a photo / thermal latent acid generator. Phosphate [produced by Nippon Soda Co., Ltd.], HABI is 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,
2'-bisimidazole [manufactured by Wako Pure Chemical Industries, Ltd.].

<Preparation of Test Plate> Standard panel (75 × 150 mm) manufactured by Nippon Test Panel Kogyo Co., Ltd .: A galvanized steel plate (zinc light), a mild steel plate, a stainless steel plate, and an aluminum plate were used. What was polished lightly with sandpaper and then degreased with acetone was used.

<Curing Method> Examples 1 to 4 and Comparative Examples 1 to
Each putty composition was placed 4 cm wide and 3 m thick on each test plate.
m with a spatula, and a distance of 1 m using a 2KW metal halide lamp [trade name: Dynabeam 2: manufactured by Toshiba Lighting & Technology Corp .: hereinafter referred to as lamp 1], which is a light source including a wavelength in the visible light region. (Light illuminance in a wavelength range of 380 to 450 mm: 30 mW / cm ² ) for 5 minutes to cure.

<Evaluation of Putty Coating Performance> The following items of the putty coating film test pieces obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated. (1) Curability of coating film (surface and inside): After light irradiation for a predetermined time, the drying property of the coating film surface and the cured state of the inside were evaluated by finger touch. (Good: ◎, surface slightly tacky but internal curing: ○, surface tacky but internal curing: △, surface tacky and internal curing poor: ×) (2) Coating adhesion: various putty coated test plates at right angles The putty at the bent portion was evaluated. (Good: ○, slight adhesion: Δ, no adhesion: ×) (3) Abrasiveness: The coating surface of various putty coated test plates was # 40
The sample was polished with water-resistant paper and the polished state was evaluated. (Good: ○, slight adhesion to paper: △, heavy adhesion to paper, heavy polishing: ×)

Table 1 shows the amounts of the putty compositions and the results of the putty coating performance evaluation in Examples 1 to 4 and Comparative Examples 1 and 2.

[0062]

[Table 1]

Examples 5 to 7 and Comparative Examples 3 and 4 The following putty compositions were prepared and cured on a test plate, and the coating film performance was evaluated. <Preparation of Putty Composition> For Example 5, 100 parts of a vinyl ester resin [trade name: Lipoxy RF-304: manufactured by Showa Polymer Co., Ltd.], 100 parts of acrylic acid: 5 parts of AEROSIL 200: 4 copies, BYK
R605: 1.6 parts, I-819: 2.0 parts, TMP3
A: 5 parts, 2-HEMA: 10 parts, talc: 50 parts, calcium carbonate: 50 parts, and mixed with a high-speed dissolver to obtain 2 parts.
The mixture was stirred and mixed for 0 minutes to obtain a putty composition. In Examples 6 and 7 and Comparative Examples 3 and 4, the composition of the resin, the initiator and the like in Example 5 was changed to the composition shown in Table 2, and a putty composition was obtained by the same operation as in Example 5. . The second
The symbols for each formulation in the table are the same as in Table 1.

<Curing Method> Using the test plates prepared in the same manner as in Example 1, the putty compositions of Examples 5 to 7 and Comparative Examples 3 and 4 were placed on each test plate in a width of 4 cm and a thickness of 3 mm. The mixture was applied with a spatula in the form of a mountain, and light was irradiated using a lamp 1 at a distance of 1 m for 5 minutes. After putty curing, waterproof paper # 80, # 1
Polish the putty surface in the order of 50, # 240 and # 400,
A smooth surface is prepared, a commercially available acrylic urethane paint (produced by Isaam Paint) is spray-coated on the putty surface to a thickness of about 50 μm, left at 23 ° C. for 1 hour, and dried in a 60 ° C. drying oven.
After drying for a time, a coated test piece was obtained.

<Evaluation of coating film performance> The coated test pieces obtained in Examples 5 to 7 and Comparative Examples 3 and 4 were evaluated for the following items. (1) Water resistance: The obtained coated test piece was left in an oven at a temperature of 50 ° C. and a humidity of 95% for 3 days, and the presence or absence of blister was visually evaluated. (No blister: ◎, several small blisters: ○, several large blisters: △, many large and small: ×) (2) Secondary adhesion: The painted test piece after the water resistance test was bent at a right angle. The state of adhesion of the putty at the bent portion was evaluated. (Good: 、, slight adhesion: Δ, no adhesion: ×) (3) Cross-cut adhesion test: A cross-cut adhesion test was performed on the painted test piece after the water resistance test, and the state of adhesion was evaluated. (No peeling: ○, slight peeling: △, whole peeling: ×)

Table 2 shows the amounts of the putty compositions in Examples 5 to 7 and Comparative Examples 3 to 4 and the results of the evaluation of the coating film performance.

[0067]

[Table 2]

Examples 8 to 10 and Comparative Examples 5 to 6 The following primer surfacer compositions were prepared and cured on test plates to evaluate the coating film performance. <Preparation of Primer Surfacer Composition> In Example 8, a vinyl ester resin [trade name: Lipoxy R-802:
Showa Polymer Co., Ltd.]: 100 parts, acrylic acid: 5 parts,
Styrene monomer 20 parts, TMPTA: 5 parts, 2-HE
In a mixture consisting of 10 parts of MA, 10 parts of ethyl acetate,
AEROSIL 200: 2 parts, thixotropic auxiliary BYK R60
5: 0.8 part, I-819: 1.0 part, talc: 30
Parts, calcium carbonate: 20 parts, and mixed with a high-speed dissolver for 20 minutes to obtain a primer surfacer composition. Examples 9 to 10 and Comparative Examples 5 to 6
Then, the composition of the resin, the photopolymerization initiator and the like in Example 8 was changed to the composition shown in Table 3, and the same operation as in Example 8 was carried out to obtain a primer surfacer composition. The third
In the table, SM is a styrene monomer, MEK is methyl ethyl ketone, and the symbols of other compounds are the same as in Table 1.

<Preparation of Test Plate> Standard panel (75 × 150 mm) manufactured by Nippon Test Panel Co., Ltd .: A galvanized steel plate (zinc light), a mild steel plate, a stainless steel plate, and an aluminum plate were used. Polished with sandpaper and then degreased with acetone was used.

<Curing Method> Examples 8 to 10 and Comparative Example 5
Each of the primer surfacer compositions of Nos. To 6 was spray-coated on each test plate so as to have a thickness of 100 μm, and was irradiated with light using a lamp 1 at a distance of 1 m for 2 minutes to be cured.

<Evaluation of Performance of Primer Surfacer Coating Film> The test pieces of the primer surfacer coating films obtained in Examples 8 to 10 and Comparative Examples 5 to 6 were evaluated for the following items. (1) Curability of coating film: After curing by light irradiation for a predetermined time, the cured state was evaluated by dryness of the surface to the touch. (Good:
◎ 、 Slight surface tack ： △ 、 Surface tack but hardening ：
×) (2) Abrasiveness: The coating film surface of the obtained coated test piece was # 40
The sample was polished with water-resistant paper and the polished state was evaluated. (Good: ○, slight adhesion to paper: Δ, heavy adhesion to paper, heavy polishing: ×) (3) Water resistance: The obtained coated test specimen was treated at a temperature of 50 ° C. and a humidity of 95%. It was left in an oven for 3 days, and the presence or absence of blisters was visually evaluated. (No blister: ◎, several small blisters: ○, several large blisters: △, large and small: x) (4) Secondary adhesion: The painted test piece after the water resistance test was bent at a right angle. The state of adhesion of the coating film at the bent portion was evaluated. (Good: 、, slight adhesion: Δ, no adhesion: ×) (5) Cross-cut adhesion test: A cross-cut adhesion test was performed on the painted test piece after the water resistance test, and the state of adhesion was evaluated. (No peeling: ○, slight peeling: Δ, full peeling: ×) (6) Surface appearance after coating: After curing the primer surfacer, a commercially available acrylic urethane paint (manufactured by Isamu Paint Co., Ltd.) was applied to the surface. Spray 50μm thick, 23
After leaving at room temperature for 1 hour and then drying in a 60 ° C. drying oven for 1 hour, the surface appearance was evaluated. (Smooth: ○, non-smooth part: X)

Table 3 shows the amounts of the primer surfacer compositions in Examples 8 to 10 and Comparative Examples 5 to 6 and the results of the evaluation of the coating film performance.

[0073]

[Table 3]

[0074]

As is clear from the above examples, the putty or primer surfacer composition of the present invention has excellent coating performance, high curability, adhesion and polishing properties, water resistance, A coated plate excellent in secondary adhesion and grid adhesion can be obtained. In addition, the putty or primer surfacer composition of the present invention is a one-part type photo-curing type and does not require a kneading operation, so that the mixing of air bubbles is small, and curing can be performed in a short time, so that the working process time can be reduced, In addition, the adhesion to various substrates can be improved.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09D 5/34 C09D 5/34 163/10 163/10 167/06 167/06 167/07 167/07 175/16 175 / 16 F term (reference) 4J011 AA03 AA06 DA02 DA04 FA01 FB01 HB17 PA02 PA13 PB22 PC02 QA02 QA08 QB12 QB14 QB19 QB20 QB22 QB23 QB24 SA63 SA64 SA77 SA78 SA83 SA84 SA85 SA86 SA87 UA06 VA01 AB02 AB01 AB01 AB01 AB02 AB24 AB25 AE01 AE02 AE03 AG01 AG03 AG04 AG08 BA02 BA04 BA06 BA08 BA24 BA25 BA26 CA18 CB10 CC04 CD08 4J038 DD191 FA041 FA081 FA191 FA251 FA261 FA281 GA09 GA10 GA12 HA446 JA07 JA33 JA34 JA66 JB32 JC17 JC18 JC22 JC37 J0822

Claims (7)

[Claims] 1. (A) at least one radical polymerizable resin selected from unsaturated polyester resins, vinyl ester resins, polyester (meth) acrylates and urethane (meth) acrylate resins: 100 parts by weight, (B) intramolecular Radical polymerizable unsaturated compound having at least one carboxyl group: 1 to 100 parts by weight, (C) a photopolymerization initiator having photosensitivity in the visible light region and / or an organic boron compound represented by formula (1) A putty or primer surfacer composition comprising: 0.01 to 10 parts by weight of a polymerization initiator which is a combination of a compound and an acidic compound; and 0.1 to 300 parts by weight of a filler (D). Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group, a halogen atom, a substituted alkyl group, Substituted aryl group, substituted allyl group,
Represents a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a cation) 2. The putty or primer surfacer composition according to claim 1, wherein the polymerization initiator (C) is a polymerization initiator obtained by combining an organic boron compound and an acidic compound with a hexaarylbiimidazole compound. 3. The compound according to claim 1, wherein the acidic compound is a latent acid generating compound that generates an acid by light irradiation, heating, at least one action of moisture and oxygen in the air. Putty or primer surfacer composition. 4. The latent acid generating compound that generates an acid by light irradiation, heating, or at least one of the action of moisture and oxygen in the air is a sulfonium compound that generates an acid by light irradiation and / or heating. 4. The putty or primer surfacer composition according to item 3. 5. The putty or primer surfacer composition according to claim 1, wherein the photopolymerization initiator (C) having photosensitivity in the visible light region is a (bis) acylphosphine oxide type. 6. The filler according to claim 1, wherein the filler is a fine silica powder.
The putty or primer surfacer composition according to any one of the above items 5 7. The putty or primer surfacer composition according to any one of claims 1 to 5, wherein
A method for curing a putty or primer surfacer composition, comprising irradiating light having an illuminance of 20 mw / cm ² or more in a wavelength region of nm to cure the composition.